Detergent composition

ABSTRACT

1. A DETERGENT COMPOSITION COMPRISING ONE OF THE WATER-INSOLUBLE METAL SALTS OF AN AMPHOTERIC SURFACE ACTIVE AGENT WHICH ARE EXPRESSED BY THE GENERAL FORMULAS: WHEREIN: R REPRESENTS A HYDROCARBON GROUP HAVING 6-30 CARBON ATOMS; R7 REPRESENTS HYDROGEN OR CH3; M REPRESENTS AN INTEGER OF 1 TO 3; P REPRESENTS AN INTEGER OF 1 TO 2; X REPRESENTS HYDROGEN, (CH2)MCOO OR (CH2)MCOOH; X1 IS X OR NOTHING WITH THE PROVISO THAT WHEN X1 IS NOTHING THERE IS NO OH GROUP BONDED TO NITROGEN; B REPRESENTS AN INTEGER OF 1 TO 2; D REPRESENTS AN INTEGER OF 0 TO 1; Q AND R EACH REPRESENT AN INTEGER OF 0 TO 2; L (SMALL L) REPRESENTS AN INTEGER OF 0 TO 5; S REPRESENT AN INTEGER OF 1 TO 4; M REPRESENTS AN ALKALINE EARTH METAL; X, Y AND Z EACH REPRESENT AN INTEGER DETERMINED BY THE VALENCY OF THE METAL; A REPRESENTS EITHER -(CHR&#39;&#39;CHR&#39;&#39;O)PX OR   ((R-(CH(-O-(CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)Q-X-CH2)K)B-(N(-OH)(-X1)   (CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)R-X)-(CH2)S)L-N(-OH)(-A)(-(CH2)M-COOH)   -(CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)P-S)X M(Y)   ((R-(CH(-O-(CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)Q-X)-CH2)K)B-(N(-OH)(-X1)   (CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)R-X)-(CH2)S)L-N(-OH)(-A)(-(CH2)M-   COOH)-(CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)P-X)X M(Y)   ((R-(CH(-O-(CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)Q-X)-CH2)K)B-(N(-OH)(-X1)   (CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)R-X)-(CH2)S)L-N(-OH)(-A)(-(CH2)M-   COOH)-(CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)P-X)Z   AND WHICH ARE SELECTED FROM THE METAL SALTS OF AN AMPHOTERIC SURFACE ACTIVE AGENT HAVING IN THE MOLECULE THE FOLLOWING COMMON GROUP:   R-CH(-O-(CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)P-X)-CH2-   SAID WATER INSOLUBLE METAL SALT BEING BLENDED WITH AT LEAST ONE SUBSTANCE EXPRESSED BY THE GENERAL FORMULA:   X-(O-CH(-R&#39;&#39;)-CH(-R&#39;&#39;))P-N(-OH)-(CH2)M-COOH   WHEREIN: U, V AND W EACH REPRESENT AN INTEGER OF 3 TO 100; ME REPRESENTS AN ALKALINE EARTH METAL; D REPRESENTS EITHER -(CHR&#39;&#39;CHR&#39;&#39;O)UX6 OR   ((R-(CH(-O-(CH(-R&#39;&#39;)-CH(-R&#39;&#39;)-O)V-X3)-CH2)K)B-(N(-X1)(-OH)   (-CH(-R&#39;&#39;)-CH(-R&#39;&#39;-O)R-X)-(CH2)S)B-N(-X2)(-OH)(-D)-(CH(-R&#39;&#39;)   -CH(-R&#39;&#39;)-O)U-X5)2 ME(Y)   X1 AND X2 REPRESENT HYDROGEN OR (CH2)MCOO WITH THE PROVISO THAT WHEN X1 AND X2 ARE NOT (CH2)MCOO, NITROGEN WILL BE TERTIARY NITROGEN; AND X3, X4, X5, X6 AND X7 EACH REPRESENT HYDROGEN OR (CH2)MCOO.

United States Patent US. Cl. 252-548 8 Claims ABSTRACT OF THE DISCLOSURE A new detergent composition comprising, in combination, a water-insoluble metal salt of amphoteric surface active agent and a substance capable of dispersing and solubilizing this metal salt in water. This composition may be used either independently or by being included in any known detergent. In this latter instance, the detergency, bubble-forming ability and duration of bubbles of the base detergent are greatly improved. In particular, laundry which is cleansed with this composition either directly or jointly with a known detergent is invariably bestowed with an antistatic property, a resistivity to resoiling and a soil-releasability.

This is a division, of application Ser. No. 168,413, filed Aug. 2, 1971, now Pat. No. 3,719,613.

BACKGROUND OF THE INVENTION (a) Field of the invention The present invention is concerned with a detergent, and more particularly, it relates to a new detergent composition having an improved amphoteric surface active agent as its active component.

(b) Description of the prior art In general, it has been the practice to wash natural fibers and man-made fibers with either an anionic surface active agent such as a sodium salt of alkylbenzene sulfonate or a non-ionic surface active agent such as nonyl phenol ethylene oxide adduct. However, in case these known detergents were used, the fibers cleansed with such a detergent invariably presented a deteriorated hand feel and/or a loss of antistatic property. Therefore, it has been the usual practice to give the washed fibers an additional treatment with a soft-finishing agent and/or an antistatic agent. However, these properties which were thus added to the fibers disappeared when the fibers were washed again. On the other hand, in case the fibers were washed with known detergent mixed with a soft-finishing agent and an antistatic agent, the individual effects of these mixed detergents were not exhibited clearly but rather they served, in many cases, only to lowering of the activity of the detergent per se. Therefore, in case it was intended to use a soft-finishing agent and/or an antistatic agent, it was necessary to add these agents in a rinsing solution after cleansing or to subject the washed fibers to a separate treatment with these agents, and thus a great inconvenience was experienced.

The inventor had already accomplished a method of imparting an antistatic property to plastics by the inclusion-in a plastic by kneading-of a substance having the general formula:

CHzCOO x 3,850,853 Patented Nov. 26, 1974 wherein:

R represents a hydrocarbon group having 6-22 carbon atoms,

M represents a metal,

1 represents an integer, and

x, y each represents an integer determined by the valency of the said metal.

SUMMARY OF THE INVENTION The author made an extensive research in order to find means of effecting the deposition or the adsorption of the said substance having the chemical formula (I) onto the surface of a polymer-which is intended to be given an antistatic property-externally of the surface of the polymer in an aqueous solution Without kneading this substance into the polymer. By the use of anetfective dispersing agent, the author solubilized and partially dispersed a water-insoluble substance in an aqueous solution to prepare a transparent aqueous solution containing this substance in the state of being dispersed and solubilized therein. By destroying the resulting emulsion and then bonding the particles of this substance in this aqueous solution onto the surface of a polymer, the substance was deposited in an adsorbed state on the surface of the polymer externally. As a result, the author succeeded in form ing a water-insoluble molecular surface layer of the sai substance on the surface of the polymer.

According to the authors researchwhich was ref, ported in Kogyo Kagaku Zasshi, vol. 68, p. 2186, (1965 it was found that the substance having the chemical. structure (I) could be modified-in case the substance was an alkali earth metal salt such as a salt of calcium or barium-into a quite stable substance having the following chemical formula which was an acid salt of a metal salt of amphoteric surface active agent:

. detergent, but also having the capability of imparting to laundry which is cleansed with it. an antistatic property, resistivity to re-soiling and soil releasability.

Another object of the present invention is to provide a new detergent composition of the type described, which not only can be used independently as a detergent, but also which, when included in a small amount in any. known detergent, fully exhibits the aforesaid desirable effects.

Still another object of the present invention is to provide a new detergent composition of the type described, which gives laundry which is cleansed with it a longstaying antistatic property, resistivity to re-soiling and soil releasability and which, thus: can display the same useful effects for practical purposes as those exhibited by laundry which is given an additional antistatic and other treatments after being washed.

3 These as well as other objects, advantages and features of the present invention will become apparent by reading the following detailed description of the preferred embodiments.

DETAILED DESCRIPTION OF TI-HE PREFERRED EMBODIMENTS The present invention contemplates the provision of a new detergent composition which is prepared by the use of at least one of those water-insoluble metal salts of 10 amphoteric surface active agent which are expressed by the general formulas:

Hz) in C 0 O z (III) N-CH:

(CHI)mCOO x (CH2)mCOOH OHA and

HX: A

OHA

wherein:

R represents a hydrocarbon group having 6-30 carbon atoms;

R CH CH, l

k o 0HR'0HR'0),XJb R' represents hydrogen or CH m represents an integer 1-3; p represents an integer of 1 or 2; X represents hydrogen or (CI-I COO or (CH COOH;

X may be X or nothing; in the latter case there is present no OH group bonded to nitrogen; b represents an integer 1 or 2;

k represents an integer 0 or 1; 65

q, r each represents an integer 0 or 1 or 2; 1 represents an integer 0 or 1-5;

s represents an integer 1-4;

M represents an alkali earth metal;

x, y, z each repesents an integer determined by the 70 valency of the said metal; and A represents either --(CHR'CHR'O) X or R-CH-CHr- 1 (CHz)mCOO and which are selected from among the metal salts of amphoteric surface active agent having, in the molecules thereof, the following common group:

wherein:

m represents an integer 1-3;

R' represents hydrogen or CH X represents hydrogen or (CH COO; and p represents an integer 1 or 2 orra onn'm x Myz (VI) and blending the aforesaid water-insoluble metal salt to r at least one of the substances expressed by the general 1, 2, X X X X X each represents hydrogen or (CH COO (wherein: m represents an integer 1-3; at least one of X X X X X X X7 is in case X and X are not (CH COO, nitrogen will be tertiary nitrogen),

and by solubilizing and dispersing the resulting mixture in water in partially solubilized condition. This composition may be used widely as a detergent either independently or by being added in any known detergent, in each of which instances the composition will exhibit an excellent detergency, bubble formability and bubble durability for laundry which is washed with this composition, and moreover, it can give the laundry an antistatic property, a resistivity to resoiling and a soil releasability of a prolonged duration.

In other words, the detergent composition of the present invention may be regarded as a sort of polymeric electrolyte or polymeric surface active agent, and can be considered to present a dispersion system of high molecular weight micelles, in a solution, of at least one of the aforesaid substances expressed by the general formulas (III), (IV), (V) and (VI). Accordingly, the critical micelle concentration of these substances for micelle formation is very low, which appears to be in the order of Vm of the critical micelle concentration of sodium alkylbenzene sulfonate. Thus, the detergent composition of the present invention exhibits surface activity at a very low 2N (CH 5 can be used independently as a finishing agent for the purposes of antistatic treatment, anti-resoiling treatment, soilrelease treatment and/or softening treatment. Such properties of the composition of the present invention can be as equally exhibited in case it is added to known detergent compositions as is exhibited in case it is used alone. As an example of especially effective instances, this composition is added to a known carpet shampoo consisting mainly of sodium salt of alkyl sulfate. By doing so, ex: tremely stable bubbles are formed, and moreover, it is possible to have the soil components adsorb or deposit onto the surfaces of the bubbles effectively, and also, after the bubbles have been removed by a vacuum suction device, the carpet surfaces will have excellent antistatic property and soil-releasability.

As the metal in (III)(VI) in the present invention, metals other than alkali metals which form water-insoluble metal salts having a high melting point are selected as a principle. More desirably, the use of an alkali earth metal such as calcium and barium is suitable. By the use of an alkali earth metal, it should be understood that (III) and (V) can form acid salts in the form of (IV) and (VI), respectively.

Hereunder are shown typical substances in order to explain the general formula (V) in further detail.

()(CHRGHROMX X (V-1) f OH CH2)mCOO R-CH-CHZN(CHR'CHRO)DX My (CHRCHRObX 0(CHR'CHROMX X (V-2) OH cmmooo OH ommooo i l) 2 i 2 RCH-CHz-N(CHz)s N--(CHRCHRO)X My (CERCHR'O),Xi (lH/ -CH-R ownn'onn'omr O(OHROHRO),,X x we) 05f )CHzMCOO ROHCHz-N-(CHRCHR'O) X (CH2CH-R O(CHRCHR'O)X 1J)(CHRCHR'O);,X X (V-4) concentration-thereof and displays a satisfactory deter- 0H gency. Furthermore, solubilization and destruction of dis- I I persion take place at the laundry/washing solution and I CHR mvx air/washing solution interfaces, and as a result, a water- R-N My insoluble and firm mono m0lecular layer is formed by R, X adsorption of the said composition onto the surface of the laundry. Accordingly, bubbles which are firm and 'yet (0119111000 X durable are formed very easily. Along with this, a tough 0H mono-molecular layer of the substance of either (III), (IV), (V) or (V1) is formed in the same way at the sur- OH (0H2)mc0o face ofthe laundry. Thus, the laundry is imparted an RN-(CHz)i--N(CHRCHROBX My antistatic property and at the same time the laundry is HIVCHRIORX w x (V 6) effectively prevented from re-deposition thereon of the soil components, especially of oily soil, having been de- OH (01125000 tached previously therefrom, thus developing a high re- R N-(CHR'CHR'Q)DX soiling preventability or soil releasability. HZCHLR In view of the fact that this mono-molecular surface layer of the substance of (III), (IV), (V) or (VI) is in- P X (V4) soluble in'water and is firm, it is held stably at the surface OH of'the laundry in the rinse process also. Moreover, the said layer is stably held thereat continuously after the OH (CHQIHCOO (CHQMCOO laundry is dried. Thus, the layer of the said substance is R-N-(CH2),-N-(CHR'CHR'0),,X My able to impart thelaundry an antistatic property as well HWCHHOLX as a SO11 releasabihty for an extended period of time. As I such, the detergent composition of the present invention (CHE 3 O)vX X (V's) Accordingly, in order to explain the general formula (VI) in further detail, its typical substances are shown (CHz)mGOOH )CHRCHROhX R-CHCHa--N-(CHz).--- -N\ MY- cHR'oHR'm x HR'cHR'0),X]1 omen-R (CHRCHRObX x (V1.3)

(CH2)mCOO Os )CH2)mCOO )CHRCHR'ObX R-N-(HR'cHR'0 ,,X My- R'CHCHr-' N My- CHz-CH-R O(GHR'CHR'O) X CHzCH-R 0(oHR'0HR'o ,x x

(OHR'CHR'OnX x OH (CHz)mCO0H RN(CHR'OHR'O),X

on oHamooon RCH-CHT" N"(CHR'CHRIO)| X 0(CHRICHRV0)DX z 7 I (CHR'CHR CHCH R on )CHzMCOO on nmmooo I I (OHR CHE Z Wu) RN(CH2).--N-(CHRCHR'0) X (OHRGHRO),X CH -CH-R M 0H (oHR'oHR'm X x i)OH '0 0g )crmmooon 0H (GHQ-1.000 R'"N\ R-"N'(CH2)n N (CHRCHR'o)pX (CHR'CHR'O),,X (CHR'CHRO),X CHz-CH-R M O(CHROHR'O),,X z

- OH The metallic group which can be used in (VII) may I )O h consist of the same metallic group as those stated above so as to correspond to those in (111), (IV), (V) and (VI), \CHRICHR,o X respectively. However, it is also possible to utilize those metallic groups of alkali metals and non-alkali metals of (CHQNCOOH (VH7 abroad range.

Solubilization and dispersion in water may be accom- 35 plished by first heating at least one of the substances (III) through (VI)to a temperature of 80-120 C. (in case the substance is of a high melting point, it is heated ata temperature above 120 C. but about 5 C. lower 40 than its melting point) in either anhydrous state or hydrous state, thereafter adding thereto a substance of (VII) 'heated to'the'same temperature while stirring the mixture thoroughly and cooling same down to 80-90 C., and 45 adding a predetermined amount of water of the same tem perature, followed by a thorough stirring and cooling the invention may be obtained by adding to the aforesaid composition a metal salt (such as a salt of lithium, po-

tassium or calcium) of acylated amino acid or other surface active substances.

EXAMPLE 1 N-CH2 CnHzsC N-CH Ca HO CHzCOO CHZOHZOH 2 10 parts by weight of a compound having the abovementioned structural formula were heated at 100 C. and melted. While stirring, 2.2 parts of a substance selected from those having the structural formulas (A) through (F) mentioned below and held at the same temperature were added thereto to melt the added substance uniformly. Then, 87.8 parts of boiling water which was prepared separately were added little by little while stirring to dilute the mixture. After the completion of theaddition, the resulting mixture was passed once through a homogenizer a w s 9 .49. npr m erat ra. resu t. a paste-like composition was obtained.

resulting mixture to room temperature. Desirably, this (oHzcmmwH I Q; mixture is further passed throughacolloid mill orahomo 50 C(CHtOHZWWH j' (A) genizer in order to obtain a much better and more stable 011 0132000 aqueous dispersability. C14HCEFOHPPFWEUHWMH An even more desirable composition of the present W M 2 2 M 2 (B) 0H CHzQOO CzuHqa-CH-CH N(CH2)3NCHzCHC H4 Ca cnzcrnowH -(C H CH O)wH 0 oH,oH,0 H omomomn c OH I CHzCOO 1o z1CHCH -N(CH2CH O)15H owmomomn enroll-01 ml Ca Ct-mama (D) OH I 1 I K 37 I(CH ZCHQO)IEH (Q 2CH2 )1s CHZCOO 2 OH omooo OH omooo I I Cia a1N (C 2)aN(CH2CHzO)2oH Ca I ongomomu 2 2 )2oH l Pieces of knitted fabric made of acrylic fibers (a product of Mitsubishi Rayon Co., Ltd. of Japan, marketed under the trade name of Vonnel) were allowed to sustain deposition thereon of an oily soil consisting of liquid paraflinzsoya bean oil=1:1. Thereafter, these soiled pieces of knitted fabric were washed by an electric washing machine. The result is shown in Table 1.

TAB LE 1 Deter- Antistatlc property gency of oily Half soil time of Softness (perleakage Surface (hand Detergent cent) (sec.) resistivity (S2) feel) 97 0. 1 1. 1X10 Soft. 98 0. 1 2. 3X10 Do. 98 0. 1 4. 1X10 Do. 97 0. 1 3. 3X10 Do. 96 0. 1 5. 1X10 D0. 97 0. 1 1 1X10 Do. Commercial heavy duty 72 10" Rigid detergent (No.2).

REMARKS.The composition of the commercial heavy duty detergent No. 2 is Sodium salt of linear alkylbenzene sulfonate 26%, sodium salt of tripoly phosphoric acid 24%, sodium disllicate 5%, soda ash 5% and Glaubers salt 40%.

EXAMPLE 2 N-CH:

C "Has- N--CH U QF N-CHg Ca N-CH:

CHzCHzOH CHzCHzOH CHzOOO 2 CHzCOOH 2 HO H0 parts by weight of a compound having the above mentioned structural formula were blended with 2 parts of a compound selected from (A) through (F) used in Example 1 in the same manner as that described in Example 1. The resulting mixture was diluted with 88 parts of water and a paste-like composition was prepared. In the same way as that in Example 1, a washing test was conducted. The result is shown in Table 2.

R represents a saturated hydrocarbon group having 18- 26 carbon atoms To 8 parts by weight of a substance having the abovementioned structural formula were blended 2 parts of a compound selected from (A) through (F) in the method similar to that described in Example 1. The resulting mixture was diluted with 90 parts of water and a liquidous composition was prepared. In the same way as that in Example 1, washing test was conducted. The result is shown in Table 3.

TABLE 3 Antlstatic property Deter- Softgency of Half time Surface ness Type of (VII) used oily soil of leakage resistivity (hand in the detergent (percent) (sec.) (:2) feel) 92 0.1 23x10" Soft. 93 0.1 1.1 10 Do. 96 0.1 3.2x10 Do. 91 0.1 53x10 Do. 96 0.1 731x10 Do. F 94 0.1 6.8X10 Do. Commercial heavy 72 10" Rigid.

duty detergent.

EXAMPLE 4 0H CHzCHzOH R-CH-CHz-N Ca H CHzCHzOH CHzCOO 2 wherein:

R represents a saturated hydrocarbon group having 18- 26 carbon atoms To 8 parts by weight of a compound having the abovementioned structural formula were added 2 part of a compound selected from (A) through (F) in the same manner as that described in Example 1, followed by dilution with parts of water, and a liquidous composi tion was prepared. In the same way as that in Example 1, a washing test was conducted. The result is shown in Table 4.

TABLE 4 Antlstatic pro erty Deterp Softgency of Half time Surface ness Type of (VII) used oily soil of leakage resistivity (hand in the detergent (percent) (sec.) (9) feel) 96 0.1 151x10 Soft. 97 0.1 315x10 Do. 98 0.1 1.0Xl0" Do. 0.1 415x10 Do. 94 0.1 32x10 Do. 96 0.1 6.1X10 Do. 00 y 72 m 10 Rigid.

duty detergent.

EXAMPLE 5 0H CHzCOO R-CH-CH2NCH2CHzN-CHzCHzOH Ca OCHzCHrOH CHaCHzOH CHr-CH-R CHzCH OH wherein:

R represents a saturated hydrocarbon group having 14-16 carbon atoms.

To 7 parts by weight of a substance having the abovementioned structural formula were blended 3 parts of a compound selected from (A)-(F) in Example 1 in the same manner as described therein, followed by dilution with 90 parts of water, and a liquidous composition was prepared. A washing test was conducted in the same manner as that in Example 1. The result is shown in Table 5.

TABLE 5 Antistatlc pro erty Deterp Softgency of Half time Surface ness Type of (VII) used oily soil of leakage resistivity (hand in the detergent (percent) (sec.) (S2) feel) 91 0.1 a6 10 Soft. 90 0.1 9.2 10 Do. 93 0.1 1.0 10 Do. 92 0.1 6.8X10 Do. 95 0.1 3.3 10 Do. 90 0.1 2.9mm Do. Commercial heavy 72 10" Rigid duty detergent.

13 EXAMPLE 6 wherein:

R represents a saturated hydrocarbon having 18-26 carbon atoms.

To 7 parts by weight of a compound having the abovementioned structural formula were blended 3 parts of a compound selected from (A) through (F) in the same manner as that in Example 1. By diluting the mixture with 90 parts of water, the desired composition was prepared. In the same manner as that in Example 1, washing test was conducted, the result of which is shown in Table 6.

To 8 parts by weight of a compound having the abovementioned structural formaul were blended 2 parts of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by diluting with 90 parts of water, and as a result, the desired composition was prepared. Washing test was conducted in the same manner as that in Example 1. The result of the test is shown in Table 7.

TABLE 7 Antistatic property Half time of leakage (sec.)

Detergency of oily soil (percent) Soft- Surface ness resistivity (hand (a) feel) 1.0)( Soft.

8.2)(10 Do. 6.4)(10 1.0)(10 7.1)(10 6.0 10 Do.

10 Rigid.

Type of (VII) used in the detergent he duty detergent.

I CHzOH OH To 9 parts by weight of a compound having the abovementioned structural formula was blended 1 part of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by dilution with 90 parts of water, and thus the desired composition was prepared. The result of washing test conducted in the 14 same manner as that in Example 1 is shown in the following Table 8.

TABLE 8 .Antistatic pro ert Deterp y Softgency of Halftime Surface ness Type of (VII) used oily soil of leakage resistivity (hand in the detergent (percent) (sec.) (S2) feel) 0.1 ILOXIO Soft. 89 0. 1 3.2)(10 D0. 90 0.1 4.4X10 Do. 91 l). 1 1.2)(10 D0. 90 t). 1 1.0)(10 Do. 92 0.1 3.6X10 Do. Commercial heavy 72 10" Rigid.

duty detergent.

EXAMPLE 9 0H CH2COO CisHa'lN-(CH2CH20)zH Ca CHzCH-R (CH2CHzO)2H 2 wherein:

R represents a saturated hydrocarbon having 18-26 carbon atoms To 8 parts by weight of a compound having the abovementioned structural formula were blended 2 parts of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by dilution with 90 parts of water in the same manner as that in Example 1, and thus the desired composition was prepared. Washing test was conducted in the same manner as that in Example 1. The result of this test is shown in Table 9.

TABLE 9 Antlstatic r0 ert Deterp p y Softgency of Half time Surface ness Type of (VII) used oily soil of leakage resistivity (hand in the detergent (percent) (sec.) (9) feel) 92 0.1 3.6)(10 Soft. 92 l). 1 8.2X10 Do. 91 ill 3.6Xl0 Do. 93 l). 1 113x10" D0. 90 ll. 1 1.5)(10 D0. 93 l). 1 3.0X10 Do. Commercial heavy 72 w 10 Rigid duty detergent.

EXAMPLE 10 0% C/HzCOO OH CHzCOO CraHwN-(CH2)3NCH2CH2OH Ca CH1; CH-R CHzCHzOH OCHzCHzOH wherein:

R represents a saturated hydrocarbon having 1416 carbon atoms To 9 parts by weight of a compound having the abovementioned structural formula was added 1 part of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by dilution with 90 parts of water, and thus the desired composition was prepared. Washing test was conducted in the same manner as that in Example 1. The result of this test is as shown in Table 10.

TABLE 10 Antistatic property Deter- Softgency of Half time Surface ness Type of (VII) used oily soil of leakage resistivity (hand in the detergent (percent) (sec.) (S2) feel) 88 0.1 7.8X10 Soft. 91 I). 1 6.6X10 Do. 93 0. 1 5.0X10 Do. 90 D. 1 4.6)(10 Do. 90 0. 1 1.1X10 Do. 91 f). 1 3.6X10 Do. Commercial heavy 72 w 10" Rigid.

duty detergent.

wherein R represents a saturated hydrocarbon having 18-26 carbon atoms To 9 parts by weight of a compound having the abovementioned structural formula was added 1 part of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by dilution with 90 parts of water, and thus the desired composition was prepared. A washing test was conducted in the same manner as that in Example 1. As a result, superior hand feel, detergency and antistatic property as compared with those ofcommercial heavy dut detergents were demonstrated as in Example 3.

EXAMPLE 12 CHzCHzOH R--CHCH2N Ca.-

H OHzOHzOH CH2CO O 2 CHzCHzOH RCHCH2N H CHzCHzOH 01120 O OH 2 wherein R represents a saturated hydrocarbon having 18-26 carbon atoms To -8 parts by weight of a compound haping the abovementioned structural formula were blended 2 parts of a compound selected from (A) through (E) used in Example 1, followed by being diluted with 90 parts of water, and thus the desired liquidous composition was prepared. A washing test was conducted in the same manner as that in Example 1. The result was that superior hand feel, detergency and antistatic property were demonstrated as in the case of Example 4.

wherein:

R represents a saturated hydrocarbon having 18-26 carbon atoms To 8 parts by weight of a compound having the abovementioned structural formula was blended 1 part of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by dilution with parts of water, and thus the desired liquidous composition was prepared. In the same manner as that in Example 1, a washing test was conducted. The result was that superior hand feel, detergency and antistatic property same as those in Example 5 were noted.

EXAMPLE 14 R-CH-CHzN-OH2OH2OH H CHz-OH-R wherein:

R represents a saturated hydrocarbon having 18-26 carbon atoms To 7 parts by weight of a compound having the abovementioned structural formula were blended 3 parts of a compound selected from (A) through (F) of Example 1, followed by being diluted with 90 parts of water to prepare the desired composition. In the same manner as that in Example 1, a washing test was conducted. The result showed superior effects as in Example 6.

EXAMPLE 15 OH OH CH3 CH CisHa- NCHzC }HOH Ca CmHwN-CHzHOH OHZCHOH CHZCHOH CH2COOH CHzCOO CH: 2 3 7 To 8 parts by weight of a compound having the abovementioned structural formula were blended 2 parts of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by dilution with 90 parts of water to prepare the desired composition. A Washing test was conducted with this composition. The result was that superior effects as those in Example 7 were exhibited.

To 9 parts by weight of a compound having the abovementioned structural formula was added 1 part of a compound selected from (A) through (E) in the same manner as that of Example 1, followed by dilution with 90 parts of water. Thus, desired composition was prepared. This was subjected to a washing test, with the result that superior efiects as those in Example 8 were noted.

EXAMPLE 17 OH omooo omrrw-N omomo)zn om-on-n (CH2CH2O)H 2 OH CHZOOO OH CHzCOO C1 l[a1 N- (CHz)3 N-CHzCHzOH Cacmonn omomon oomomorr 0H crnooon OH omooon C H;n N -(CH2)a NCHzCH OH om-cn-n wherein:

R represents a saturated hydrocarbon having 1416 carbon atoms To 9 parts by weight of a compound having the abovementioned structural formula was added 1 part of a compound selected from (A) through (F) in the same manner as that in Example 1, followed by dilution with 90 parts of water to prepare the desired composition. A washing test was conducted by the use of this composition. The result showed as satisfactory effects as those demonstrated in Example 10.

EXAMPLE 19 Commercial detergent used in this Example had the following composition:

12% of sodium salt of linear alkylbenzene sulfonate, 15% of sodium tripoly-phosphate and an amount of Glaubers salt which was increased to 63%. To a batch of this commercial detergent compositon was added 10% of a composition selected from those obtained in the abovementioned Examples, i.e., the composition containing (B) and the composition containing (E) in Example 1; the composition containing (B) and the composition containing (E) in Example 2; the composition containing (B) and the composition containing (E) in Example 4; and the composition containing (B) and the composition containing (E) in Example 12. They were added, respectively, one for one batch. Thus, detergent compositions were prepared. By the use of these respective detergent compositions, washing tests were conducted on pieces of soiled polyester cloth (these pieces of cloth-product of-Teijin Co., Ltd. of Japanwere attached to the inner side of the collar of shirts and worn by persons consecutively for a Week to become soiled) in the same manner as that de- 18 scribed in Example 1. The result of these tests is shown in Table 11.

TABLE 11 Anistatic property Hall Percenttime of Softness age of S011 leakage Surface (hand Detergent removed (sec.) resistivity (S2) feel) (B), Example 1 98 0.1 2. 0X10 Soft. (E), Example 1 98 0.2 4. 5X10 Do. (B), Example 2 97 0. 2 7. 3X10 Do. (E), Example 2.. 96 0.3 1. 0 10 Do. (B), Example 4 98 0.1 8. 6x10 Do. (E), Example 4 97 0.1 5. 0X10 D0. (B), Example 12 97 0. 4 8. 0X10 Do. (E), Example 12 98 0. 5 1.0)(10 D0. Commercial heavy 76 00 10" Rigid.

duty detergent.

EXAMPLE 20 Carpet cleaning solution having the following two types of compositions were prepared.

Detergent composition of the present invention Percent Composition of the invention 0.1 Sodium salt of lauryl sulfate 0.425 Lauroyl diethanolamine 0.15 Water Balance Control composition Percent Sodium salt of lauryl sulfate 0.5 Lauroyl diethanolamine 0.15 Water Balance By the use of these two types of detergent compositions, soiled light brown carpets made of nylon fibers were washed according to ordinary carpet washing method, i.e., bubble formation-brushing-leaving them lying in bubblesvacuum suction. The result of the washing test is as shown in Table 12.

TABLE 12 Moisture re- Hall Degree of movability time of soil reupon compleleakage Re-soil Detergent moved tion of washing (see) (days) (B), Example 1 Good Fresh and light: 1. 2 67 dried quickly. (E), Example 1 -do. r do 1.0 55 (B), Example 2 0. 5 70 (E), Example 2 0.1 65 (B), Example 4-. 0.6 55 (E), Example 4-. 1. 0 60 (B), Example 12 1.0 65 (E), Example 12 do do 0.8 70 Control Still had Very wet when w 18 some soil. touched.

Carpets were laid at the entrance of a building. The number of days required for being soiled to almost the same degree as noted before being wash ed was calculated from floor test. The carpets were, however, cleaned once every day by an electric cleaner.

EXAMPLE 121 Hair shampoo compositions were prepared by adding 10% of the compositions of the present invention (containing of water) to batches of the following hair shampoo composition:

Hair was washed with these compositions, respectively. The result is shown in Table 13.

(B), Example 1 (E), Example 1 (B), Example 2 EXAMPLE 22 Those compositions shown in the foregoing Examples were further diluted to A with water. Pieces of a knitted fabric made of Nylon-6 fibers (product of Toray Co., Ltd. of Japan) were immersed in the solution at the bath ratio of 1:30, at 30 C. for minutes. Then, the pieces of fabric were squeezed to about 50%. After being air-dried at room temperature, they were felt to determine the softness. Thereafter, the treated pieces of fabric were washed with a commercial heavy duty detergent under the washing conditions stated in the Example. Thereafter, they were soaked for 12 hours in a sufliciently soiled solution prepared by washing soiled underwear with a commercial heavy duty detergent until bubbles ceased to form. After being air-dried at room temperature they were determined of the soil additional density (SAD) (log R /R wherein: R represents reflectance before being soiled, and R represents reflectance after being soiled). The result is shown in Table 14. From this Table, it is known that the compositions of the present invention impart soft feel and antistatic property to laundry.

What is claimed is:

1. A detergent composition comprising one of the water-insoluble metal salts of an amphoteric surface active agent which are expressed by the general formulas:

20 wherein: R represents a hydrocarbon group having 6-30 carbon atoms; R represents hydrogen or CH m represents an integer of 1 to 3; p represents an integer of 1 to 2; X represents hydrogen, (CH COO or (CH COOH; X is X or nothing with the proviso that when X is nothing there is no OH group bonded to nitrogen; b represents an integer of l to 2; k represents an integer of 0 to 1; q and r each represent an integer of 0 to 2; 1 (small L) represents an integer of 0 to 5; s represents an integer of 1 to 4; M represents an alkaline earth metal; x, y and z each represent an integer determined by the valency of the metal; A represents either -(CHR'CHR'O) X or R-CH-CHz- (CHR'GHRm X and which are selected from the metal salts of an amphoteric surface active agent having in the molecule the following common group:

said water insoluble metal salt being blended with at least one substance expressed by the general formula:

I May (VII) wherein:

u, v and w each represent an integer of 3 to Me represents an alkaline earth metal;

D represents either -(CHR'CHRO) X or X and X represent hydrogen or (CH COO' with the proviso that when X and X are not (CH COO, nitrogen will be tertiary nitrogen; and

X X X X and X each represent hydrogen or (CH COO.

2. A detergent composition according to claim 1, in which the said water-insoluble metal salt is one expressed by the general formula (V).

3. A detergent composition according to claim 1, in which the said water-insoluble metal salt is one expressed by the general formula (VI).

21 22 4. A detergent composition comprising the detergent 8. A detergent composition consisting essentially of composition of claim 1 blended in an alkylbenzene sulfothe blend of salts of claim 1.

nate or aluryl sulfate detergent composition.

5. A detergent composition comprising the detergent References Cted composition of claim 2 blended in an alkylbenzene sulfo- 5 UNITED STATES PATENTS nate or lauryl sulfate detergent composition. 3,660,142 5/1972 Kasugai 260 501 1 B 6. A detergent composition comprising the detergent composition of claim 3 blended in an alkylbenzene sulfo- LEON ROSDOL, Primary Examlnel nate or lauryl sulfate detergent composition. E, ROLLINS, Assistant Examiner 7. An aqueous composition comprising the detergent 10 composition of claim 1 being at least partially solubilized US or dispersed in water. 252-528, 547; 2'60-501.13 

1. A DETERGENT COMPOSITION COMPRISING ONE OF THE WATER-INSOLUBLE METAL SALTS OF AN AMPHOTERIC SURFACE ACTIVE AGENT WHICH ARE EXPRESSED BY THE GENERAL FORMULAS: WHEREIN: R REPRESENTS A HYDROCARBON GROUP HAVING 6-30 CARBON ATOMS; R7 REPRESENTS HYDROGEN OR CH3; M REPRESENTS AN INTEGER OF 1 TO 3; P REPRESENTS AN INTEGER OF 1 TO 2; X REPRESENTS HYDROGEN, (CH2)MCOO OR (CH2)MCOOH; X1 IS X OR NOTHING WITH THE PROVISO THAT WHEN X1 IS NOTHING THERE IS NO OH GROUP BONDED TO NITROGEN; B REPRESENTS AN INTEGER OF 1 TO 2; D REPRESENTS AN INTEGER OF 0 TO 1; Q AND R EACH REPRESENT AN INTEGER OF 0 TO 2; L (SMALL L) REPRESENTS AN INTEGER OF 0 TO 5; S REPRESENT AN INTEGER OF 1 TO 4; M REPRESENTS AN ALKALINE EARTH METAL; X, Y AND Z EACH REPRESENT AN INTEGER DETERMINED BY THE VALENCY OF THE METAL; A REPRESENTS EITHER -(CHR''CHR''O)PX OR 